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Argonne National Laboratory Site Environmental Report (CY2020)

This report discusses the status and the accomplishments of the environmental protection program at Argonne National Laboratory for calendar year 2020. The status of Argonne environmental protection activities with respect to compliance with the various laws and regulations is discussed, along with environmental management, sustainability efforts, environmental corrective actions, and habitat restoration. To evaluate the effects of Argonne operations on the environment, samples of environmental media collected on the site, at the site boundary, and off the Argonne site were analyzed and compared with applicable guidelines and standards. A variety of radionuclides were measured in air, surface water, groundwater, and bottom sediment samples. In addition, chemical constituents in surface water, groundwater, and wastewater were analyzed. External penetrating radiation doses were measured, and the potential for radiation exposure to off site population groups was estimated. Results are interpreted with respect to the origin of the radioactive and chemical substances (i.e., natural, Argonne, and other) and are compared with applicable standards intended to protect human health and the environment. A U.S. Department of Energy (DOE) dose calculation methodology, based on International Commission on Radiological Protection (ICRP) recommendations and the U.S. Environmental Protection Agency’s (EPA) CAP 88 Version 4.1 computer code, was used in preparing this report.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Argonne National Laboratory Site Environmental Report for Calendar Year 2021

This report discusses the status and the accomplishments of the environmental protection program at Argonne National Laboratory for calendar year 2021. The status of Argonne environmental protection activities with respect to compliance with the various laws and regulations is discussed, along with environmental management, sustainability efforts, environmental corrective actions, and habitat restoration. To evaluate the effects of Argonne operations on the environment, samples of environmental media collected on the site, at the site boundary, and off the Argonne site were analyzed and compared with applicable guidelines and standards. A variety of radionuclides were measured in air, surface water, groundwater, and bottom sediment samples. In addition, chemical constituents in surface water, groundwater, and wastewater were analyzed. External penetrating radiation doses were measured, and the potential for radiation exposure to off site population groups was estimated. Results are interpreted with respect to the origin of the radioactive and chemical substances (i.e., natural, Argonne, and other) and are compared with applicable standards intended to protect human health and the environment. A U.S. Department of Energy (DOE) dose calculation methodology, based on International Commission on Radiological Protection (ICRP) recommendations and the U.S. Environmental Protection Agency’s (EPA) CAP 88 Version 4.1 computer code, was used in preparing this report.

54 ENVIRONMENTAL SCIENCES↗

Argonne National Laboratory Site Environmental Report for Calendar Year 2022

This report discusses the status and the accomplishments of the environmental protection program at Argonne National Laboratory for calendar year 2022. The status of Argonne environmental protection activities with respect to compliance with the various laws and regulations is discussed, along with environmental management, sustainability efforts, environmental corrective actions, and habitat restoration. To evaluate the effects of Argonne operations on the environment, samples of environmental media collected on the site, at the site boundary, and off the Argonne site were analyzed and compared with applicable guidelines and standards. A variety of radionuclides were measured in air, surface water, groundwater, and bottom sediment samples. In addition, chemical constituents in surface water, groundwater, and wastewater were analyzed. External penetrating radiation doses were measured, and the potential for radiation exposure to off site population groups was estimated. Results are interpreted with respect to the origin of the radioactive and chemical substances (i.e., natural, Argonne, and other) and are compared with applicable standards intended to protect human health and the environment. A U.S. Department of Energy (DOE) dose calculation methodology, based on International Commission on Radiological Protection (ICRP) recommendations and the U.S. Environmental Protection Agency’s (EPA) CAP 88 Version 4.1 computer code, was used in preparing this report.

54 ENVIRONMENTAL SCIENCES↗

Argonne National Laboratory Site Environmental Report for Calendar Year 2023

This report discusses the status and the accomplishments of the environmental protection program at Argonne National Laboratory for calendar year 2023. The status of Argonne environmental protection activities with respect to compliance with the various laws and regulations is discussed, along with environmental management, sustainability efforts, environmental corrective actions, and habitat restoration. To evaluate the effects of Argonne operations on the environment, samples of environmental media collected on the site, at the site boundary, and off the Argonne site were analyzed and compared with applicable guidelines and standards. A variety of radionuclides were measured in air, surface water, groundwater, and bottom sediment samples. In addition, chemical constituents in surface water, groundwater, and wastewater were analyzed. External penetrating radiation doses were measured, and the potential for radiation exposure to off site population groups was estimated. Results are interpreted with respect to the origin of the radioactive and chemical substances (i.e., natural, Argonne, and other) and are compared with applicable standards intended to protect human health and the environment. A U.S. Department of Energy (DOE) dose calculation methodology, based on International Commission on Radiological Protection (ICRP) recommendations and the U.S. Environmental Protection Agency’s (EPA) CAP 88 computer code, was used in preparing this report.

54 ENVIRONMENTAL SCIENCES↗

Sample Identifiers and Metadata Reporting Format for Environmental Systems Science

The ESS-DIVE sample identifiers and metadata reporting format primarily follows the System for Earth Sample Registration (SESAR) Global Sample Number (IGSN) guide and template, with modifications to address Environmental Systems Science (ESS) sample needs and practicalities (IGSN-ESS). IGSNs are associated with standardized metadata to characterize a variety of different sample types (e.g. object type, material) and describe sample collection details (e.g. latitude, longitude, environmental context, date, collection method). Globally unique sample identifiers, particularly IGSNs, facilitate sample discovery, tracking, and reuse; they are especially useful when sample data is shared with collaborators, sent to different laboratories or user facilities for analyses, or distributed in different data files, datasets, and/or publications. To develop recommendations for multidisciplinary ecosystem and environmental sciences, we first conducted research on related sample standards and templates. We provide a comparison of existing sample reporting conventions, which includes mapping metadata elements across existing standards and Environment Ontology (ENVO) terms for sample object types and environmental materials. We worked with eight U.S. Department of Energy (DOE) funded projects, including those from Terrestrial Ecosystem Science and Subsurface Biogeochemical Research Scientific Focus Areas. Project scientists tested the process of registering samples for IGSNs and associated metadata in workflows for multidisciplinary ecosystem sciences. We provide modified IGSN metadata guidelines to account for needs of a variety of related biological and environmental samples. While generally following the IGSN core descriptive metadata schema, we provide recommendations for extending sample type terms, and connecting to related templates geared towards biodiversity (Darwin Core) and genomic (Minimum Information about any Sequence, MIxS) samples and specimens. ESS-DIVE recommends registering samples for IGSNs through SESAR, and we include instructions for registration using the IGSN-ESS guidelines. Our resulting sample reporting guidelines, template (IGSN-ESS), and identifier approach can be used by any researcher with sample data for ecosystem sciences.

54 ENVIRONMENTAL SCIENCES↗

Applications of Hyporheic Zone Sampling for Assessing VOC Plume Engineered Remediation and Natural Attenuation Effectiveness - 20414

Determining the efficacy of engineered remedial actions and/or natural attenuation as an acceptable EPA Record of Decision (ROD) must address long-term temporal and spatial variability. Since final plume downslope destinations are aquifers and related surface streams and rivers, hyporheic zone sampling is essential. Comprehensive hyporheic sampling documents plume groundwater remediation prior to upwelling into stream benthic strata and natural attenuation within this dynamic zone itself. Our intensive sampling of the Savannah River Site (SRS) Chemical, Metals, and Pesticides (CMP) Pits VOC plume-fringe from 2005 to 2018 documented PCE natural attenuation and effectiveness of In Situ Thermal Treatment (ISTT). Most plume hyporheic upwelling was delimited to a 20 m inflow reach along Pen Branch. Our study utilized corroborative sampling methodologies: ambient hole-water grab samples: passive diffusion bags (PDB); and hole-core sediment samples to confirm station to station spatial and temporal trends. VOC hot spot detections were confirmed from both groundwater and soil core samples. VOC pathways through the Pen Branch hyporheic zone were assessed at hole-installation using sequential soil samples from augered cores and grab-samples of hole-bottom water. Longer term, composite water samples were collected from PDBs deployed for a minimum two-week equilibration period. Soil samples were collected from the 15 and 65 cm core levels in December 2017 and June 2018 at six stations. Additional core depths of 40 and 85 cm were sampled in June 2018 at the highest VOC station (5DB80). All samples were analyzed in an EPA certified lab by purge and trap GC-MS. Effectiveness of previous ISTT and soil vapor extraction (SVE) for this CMP Pits PCE plume, was clearly documented by significant downward trends in VOC at hyporheic zone stations prior to December 2015. Achieving final stage conversions of PCE daughter products to ethene and CO{sub 2} may be limited depending upon suitable interactions between hyporheic zone sediment morphology, hydrology, and redox conditions. Because declines in VOC daughter products at our hyporheic stations may also be caused by physical actions of dilution and dispersion rather than true biochemical dechlorination, full quantification of natural attenuation requires the use of compound-specific isotope ratio analysis (CSIA) and microbial 16S rRNA with qPCR. To assist these next-phase efforts, a natural attenuation index (NAI) was used to help produce quicker, more cost-effective decision making for locating CSIA and microbial sampling efforts. The NAI used natural logarithm transformed GC-MS results for station VOC degradation compounds versus VOC parent compounds. Wide differences were observed between stations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Argonne National Laboratory Site Environmental Report (CY2019)

This report discusses the status and the accomplishments of the environmental protection program at Argonne National Laboratory for calendar year 2019. The status of Argonne environmental protection activities with respect to compliance with the various laws and regulations is discussed, along with environmental management, sustainability efforts, environmental corrective actions, and habitat restoration. To evaluate the effects of Argonne operations on the environment, samples of environmental media collected on the site, at the site boundary, and off the Argonne site were analyzed and compared with applicable guidelines and standards. A variety of radionuclides were measured in air, surface water, groundwater, and bottom sediment samples. In addition, chemical constituents in surface water, groundwater, and wastewater were analyzed. External penetrating radiation doses were measured, and the potential for radiation exposure to off-site population groups was estimated. Results are interpreted with respect to the origin of the radioactive and chemical substances (i.e., natural, Argonne, and other) and are compared with applicable standards intended to protect human health and the environment. A U.S. Department of Energy (DOE) dose calculation methodology, based on International Commission on Radiological Protection (ICRP) recommendations and the U.S. Environmental Protection Agency’s (EPA) CAP-88 Version 4 computer code, was used in preparing this report.

54 ENVIRONMENTAL SCIENCES↗

Data Report: UT-GOM2-1 Lithostratigraphic Core Description Logs at Site GC 955, Holes H002 and H005

Lithostratigraphic core description provides a record of the stratigraphic variation in composition, texture, and sedimentary structure preserved in marine sediment cores. Here we present graphical lithostratigraphic core description logs for pressure cores collected during the 2017 UT GOM2-1 Expedition. The cores summarized here were those that were not retrieved under pressure, but nevertheless recovered some sufficient, intact strata that represent the host lithology across the Green Canyon (GC) 955 gas hydrate reservoir. Our results here represent visual core descriptions and include split core photos and location data for samples collected during core description.

03 NATURAL GAS↗

EERC Final Topical Report – Findings on Subtask 3.2 – Produced Water Management Through Geologic Homogenization, Conditions, and Reuse

The Energy & Environmental Research Center (EERC) was awarded a contract by the North Dakota Industrial Commission (NDIC) Oil and Gas Research Program (NDIC No. G-051-101) to conduct a study on the recycling of water used in oil and gas operations, also known as produced water, from oil- and gas-producing regions of North Dakota as directed by Section 19 of North Dakota House Bill 1014. This final report provides a compilation of results of the study, which include regulatory, scientific, technological, and feasibility methods and considerations associated with North Dakota produced water management. The report provides a synopsis of this project’s previously submitted produced water assessment report entitled “Produced Water Management and Recycling Options in North Dakota” (Energy & Environmental Research Center, 2020), with updated values provided as appropriate. The report provides the results from the investigation of a novel produced water management strategy, referred to as geologic homogenization, conditioning, and reuse (GHCR), which aims to use a subsurface geologic formation as a natural medium for managing produced water recycling and reuse. Water management is a significant technical and economic challenge for sustainable oil and gas production, and water volumes are intrinsically linked to oil production volumes. North Dakota oil production rose to over 1.5 million barrels (MMbbl)/day in 2019, and despite a downturn in oil price in early 2020, North Dakota oil production has recovered to 1.1 MMbbl/day as of August 2021. Bakken petroleum system development between 2008 and 2020 has resulted in a nearly fourfold increase in produced water volumes to 642 MMbbl/yr in 2020 after peaking at 740 MMbbl/yr in 2019 and a fivefold increase in saltwater disposal (SWD) volumes to 565 MMbbl/yr in 2020 after a peak of 682 MMbbl/yr in 2019. Produced water and SWD volumes are forecasted to double by 2030. SWD is the primary method of produced water management used in North Dakota, with approximately 95% of the SWD volume occurring through subsurface injection into sandstones of the Dakota Group (Dakota). Localized pressurization of the Dakota resulting from SWD and projected increases in produced water volumes could impact the economics of North Dakota oil production. As a result, there is an emerging need to pursue alternative produced water management approaches, including recycling and reuse. While produced water recycling is not yet widespread, commercial operators are making strides in overcoming the technical challenges of using high salinity produced water in completion operations (Marathon Oil, 2020). As water management continues to be a key focal point in companies’ environmental, social, and governance (ESG) initiatives, focus on water management, including recycling, will likely continue to increase. Laboratory column testing, field sample collection, geologic modeling and numerical simulation, and techno-economic analysis all indicate that GHCR could feasibly be implemented as a potential water management option. Laboratory column testing and field sample collection indicate that the Inyan Kara sandstone and native formation fluid are capable of homogenizing with the Bakken produced water to a point where the fluid composition appears to stabilize. Extracting that stabilized fluid could be considered homogeneous and capable of providing individual batches of hydraulic fracturing fluid. Numerical simulation results indicate that extraction of fluids from the Inyan Kara in a GHCR implementation scenario is capable of reducing formation pressure, which would help ease localized pressurization of the Inyan Kara and extend the available capacity for nearby existing SWD wells. Economic analysis indicates that there are scenarios where GHCR implementation can be a competitive or even lower-cost option than a conventional water management approach. Site-specific conditions will dictate the economic potential of GHCR, but potentially attractive sites for GHCR implementation will be those that are located above a pressurized zone of the Inyan Kara, need six or more Bakken infill wells, and face high costs for conventional SWD and/or freshwater. Based on the regulatory review, drilling into the Inyan Kara for SWD and to harness as a source water for industrial use have precedent in North Dakota, and a workable regulatory solution for GHCR seems likely. However, restrictions in the state regarding surface storage and transport of produced fluids may limit some activities, which will affect how GHCR could ultimately be implemented. In summary, this study reveals pursuing GHCR can be a viable approach to water management in North Dakota. The GHCR concept addresses some of the challenges that hinder the more traditional approaches to recycling in the industry. Furthermore, an assessment of the current landscape of water management within the state reveals the ongoing trend of increasing volumes of produced water and SWD. Projections reveal that the volumes of produced water that need to be managed are expected to double over the next decade (Energy & Environmental Research Center, 2020). With the continued development of the Bakken and continuing driving factors related to ESG initiatives, implementing a practice such as GHCR is a feasible approach to adding recycling of produced water to industry within the state. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission Oil and Gas Research Program. References Energy & Environmental Research Center, 2020, Produced water management and recycling options in North Dakota: Final Report for North Dakota Legislative Management Energy Development and Transmission Committee and North Dakota Industrial Commission. Marathon Oil, 2020, Sustainability report: https://cdn.sanity.io/files/ghcnw9z2/website/ 91744eb6ef8fbe59505a911c6b8d2e8dd9a537fa.pdf?dl (accessed November 2021).

02 PETROLEUM↗

Creating Accurate Methane Emission Inventories through Data-Driven Airborne Survey Strategies: Methods and Results from the Haynesville, Anadarko, and Permian Basins

Significantly reducing methane emissions from the oil and gas sector can decrease the rate of climate change over the next two decades, buying critical time for a global energy transition. However, emissions inventories that can be used by oil and gas operators and environmental regulators to identify optimal methane emission mitigation strategies are either based on conservative emission factor methods, or are inconsistent between studies due to differences in sampling strategies or survey technologies. We developed a new approach for methane emissions survey design that yields representative basinwide methane emissions inventories by surveying a subset of total assets in a given oil and gas basin. We identify several sampling and analysis principles, including large sample sizes, balanced sampling across oil and gas production, careful survey area definition, and a unified protocol for analysis, to be vital to producing an unbiased estimate of basin-scale emissions that can be reconciled with future studies. We further present results from deploying this strategy in two oil and gas producing regions in the United States: the Haynesville Basin in Texas and Louisiana, and the Woodford Shale in the Anadarko Basin in Oklahoma. Aerial surveys were performed in 2023 using the Insight M LeakSurveyor™ technology. Preliminary results from methane emissions detected by Insight M indicate that aerially detected emissions above roughly 30 kg(CH4)/hr by themselves contribute a fractional loss rate of 1.13% of gross gas production across oil and gas operations in the Haynesville Basin, with aerially detected emissions equivalent to 2.67% of gross gas production in the Woodford Shale. We supplement these aerial estimates with modeled emissions that are below the LeakSurveyor’s survey sensitivity using a recently published inventory-based model of methane emissions, which we update for our survey areas. We then combine our aerial detections with modeled emissions to yield methane emission distributions and inventories that incorporate the full range of potential methane emissions from the smallest to the largest. These results can be used to identify the most effective methane mitigation strategies for our study areas, and can be reconciled with future methane emissions surveys that use different technologies.

Sherwin, Evan (ORCID:0000000321804297)↗

Data Set Analysis to Reduce Uncertainty in Formula Assignments of Ultrahigh Resolution Mass Spectra

Environmental samples contain a vast array of organic compounds with diverse elemental compositions and heteroatom content. Molecular formula assignments of ultrahigh resolution mass spectra (HRMS) hold promise for elucidating the molecular composition of these compounds. However, the need to account for an assortment of heteroatoms increases the uncertainty associated with individual assignments – and ultimately the ecological, biological, and biogeochemical insights gleaned from the assignments. To address this challenge, we introduce a formula assignment strategy that leverages HRMS data sets to improve assignment confidence, filter false assignments, and mitigate bias in assignment routines. The strategy, implemented using CoreMS, first identifies the highest confidence assignment for a recurring ion in a data set by assessing the mass accuracy and isotopologue similarity of all assignments to the ion across the data set. The second component of the strategy examines the consistency of mass errors for an assigned ion throughout a data set and flags formulas with statistically unlikely deviations in mass error. Here, we illustrate the application and utility of the strategy by comparing its results against documented misassignment patterns within a set of oceanographic samples that were measured with 21 T Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Because the efficacy of our strategy improves with data set size, it is particularly useful for enhancing assignment confidence in large HRMS data sets common in studies of environmental systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of a Layered Morphology on Drip Suppression in Burning Polymers

Fire safety in polymers is critically important with products such as textiles and consumer goods, as well as materials used in construction, aerospace, transportation, and furniture. Additives used as anti-dripping and flame-retardant agents impose acute human health issues and have negative environmental impacts. With a focus on developing additive-free solutions, here we used multilayer coextrusion to fabricate layered polyethylene/polypropylene (PE/PP) films and investigated the effect of a layered morphology on dripping and burning rates. The experimental results for multilayered PE/PP samples were compared to control groups of melt blended PE/PP samples. The multilayer configuration provides two significant advantages: 154% delay in the time to the first drip and up to 87% reduction in the number of drips compared to the value for the melt blended samples with no additives. PE/PP blends with up to 2 wt % polytetrafluoroethylene, a commonly used anti-dripping agent in the industry, showed only 85% delay in the time to the first drip and about 60% reduction in the number of drips. We discovered a linear relationship between film thickness and burning rate, which allows for the use of the volumetric burning rate to normalize the effect of film thickness. No benefit in the burning rate was observed when comparing multilayered structures and conventional melt blended architectures or blends with PTFE. Annealing studies and transmission electron microscopy at areas close to the combustion zones confirmed that higher extensional viscosities induced by the layered structures and morphological changes due to the layer breakup play an important role in reducing dripping. By combining the first drip time and overall drip numbers, a parameter, “dripping index”, was defined to establish a fire safety map to simplify material comparisons. This study demonstrates that a multilayer film geometry can provide an additive-free solution to yield control over fire safety parameters in polymers.

36 MATERIALS SCIENCE↗

Product Consistency Test Results for the LXC-Series Glasses

This report provides chemical analysis of a series of Product Consistency Test (PCT) leachates from simulated nuclear waste glasses. The resulting data will be used in the development of improved property/composition models. For some of the glass leachates, minor scatter among the triplicate values of some analytes was observed. For other leachates, there were more significant differences among the triplicate values. A review of the PCT data noted that there was little difference between the normalized values on the basis of targeted or measured glass composition. Several of the canister centerline cooled study glasses have NC i values that are greater than the Hanford Tank Waste Treatment and Immobilization Plant immobilized low-activity waste constraint of 4 g/L for B and Na. The results of these glasses will help ensure the ability of advanced glass performance models to appropriately predict acceptable compositions. For many of the study glasses, heat treatment had only a marginal impact on the NC i values. The samples of the Environmental Assessment (EA) reference glass included with each PCT set had generally consistent NC i values. The release rates for boron and sodium, and for sodium and silicon were highly correlated for the study glasses, while for the other analytes, less correlation was observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calendar Year 2021 Underground Test Area Annual Sampling Letter Report Nevada National Security Site, Nevada (Rev. 1) WITH ROTC-1

This calendar year (CY) 2021 annual sampling letter report presents Plan implementation and a summary of field activities, sampling methods, well completion diagrams, and analytical laboratory results from sampling of wells on Pahute Mesa. The CY 2021 letter report also presents data from samples collected in CY 2019. These CY 2019 results were not reported in previous sampling reports because they were not available from the specialized laboratory (Lawrence Livermore National Laboratory [LLNL]) at the time of the previous reports’ publication.

54 ENVIRONMENTAL SCIENCES↗

The influence of burn severity on dissolved organic carbon concentrations across a stream network differs based on seasonal wetness conditions

Large, high-severity wildfires in many regions across the globe have increased concerns about their impacts on carbon cycling in watersheds. Altered sources of carbon and changes in catchment hydrology after wildfire can lead to shifts in dissolved organic carbon (DOC) concentrations in streams, which can have negative impacts on aquatic ecosystem health and downstream drinking-water treatment. Despite its importance, post-fire DOC responses remain relatively unconstrained in the literature, and we lack critical knowledge of how burn severity, landscape elements, and climate interact to affect DOC concentrations. To improve our understanding of the impact of burn severity on DOC concentrations, we measured DOC at 129 sites across a stream network extending upstream, within, and downstream of a large, high-severity wildfire in Oregon, USA. We collected samples across the study sub-basin during four distinct seasonal wetness conditions. We used our high-spatial-resolution data to develop spatial stream network (SSN) models to predict DOC across the stream network and to improve our understanding of the controls on DOC concentrations. Spatially, we found no obvious wildfire signal – instead, we observed a pattern of increasing DOC concentrations from the high-elevation headwaters to the sub-basin outlet, while the mainstem maintained consistently low DOC concentrations. This suggests that effects from large wildfires may be “averaged” out at higher stream orders and larger spatial scales. When we grouped DOC concentrations by burn severity group, we observed a significant decrease in the variability of DOC concentrations in the moderate and high burn severity sub-catchments. However, our SSN models were able to predict decreases in DOC concentrations with increases in burn severity across the stream network. Decreases in DOC concentrations were also highly variable across seasonal wetness conditions, with the greatest (–1.40 to –1.64 mg L –1 ) decrease occurring in the high-severity group during the wetting season. Additionally, our models indicated that in all seasons, baseflow index was more influential in predicting DOC concentrations than burn severity was, indicating that groundwater discharge can obscure the impacts of wildfire in a stream network. Overall, our results suggested that landscape characteristics can regulate the DOC response to wildfire. Moreover, our results also indicated that the seasonal timing of sampling can influence the observed response of DOC concentrations to wildfire.

54 ENVIRONMENTAL SCIENCES↗

Investigating Material Properties of Subsurface Rock Formations Modified by Engineering Mineral Precipitation (Final Scientific and Technical Report)

Montana State University’s (MSU) Energy Research Institute (ERI), in collaboration with the Center for Biofilm Engineering (CBE) and the Department of Civil Engineering (CE), has conducted a long‐term research program aimed at developing a novel cementing agent to address wellbore integrity and reduce the unwanted upward migration of fluids and greenhouse gases from the subsurface. The primary technology developed through this research program is known as ureolysis‐induced calcite precipitation (UICP), which harnesses bio‐chemical processes to precipitate calcium carbonate (CaCO 3 ). The same general process can also be called microbially-induced calcium carbonate precipitation (MICP) when microbes provide the process-catalyzing urease enzyme. Both terms are used in this report. Results have conclusively demonstrated that, if properly controlled, UICP can successfully seal fractures, high permeability zones, and compromised cement in the vicinity of wellbores and in nearby caprock. This technology has been successfully deployed to mitigate annular leakage in two test wells and over sixty commercial wells with a 100% success rate. This success in downhole deployment generates consideration of other subsurface applications where UICP could provide benefit to the energy sector, such as shale property modification for unconventional oil and gas recovery. The focus of this research project was to investigate fundamental material and mechanical properties of select shale cores and analyze how these properties change due to engineered mineral precipitation with the intent to control these properties to achieve a range of engineering objectives. Ultimately, the project aim was to identify valuable new areas where application of UICP might contribute to national energy security and environmental protection. The research workplan coupled UICP treatment of core samples, nuclear magnetic resonance (NMR) characterization, and mechanical strength testing at MSU with advanced X‐Ray micro-computed tomography (μCT) imaging and numerical modeling performed by collaborators at two national laboratories, the National Energy Technology Laboratory (NETL) and Lawrence Berkeley National Laboratory (LBNL). Experimental results are useful to inform geo-mechanical models which could be applied to predict mineralized rock formation behavior at field scale. Our findings suggest that NMR and μCT methods to detect and quantify biomineral formation in shale fractures are complementary and consistent with each other. Either could be used to estimate the volume of new mineral formed by UICP in shale fractures. The use of surfactants and guar gum to enhance biomineral precipitation in shale fractures merits further research. UICP can, under some conditions, increase the tensile strength of sealed shale fractures beyond that of the intact shale. These findings demonstrate that continued research in this area may be valuable to understanding and improving shale resource recovery techniques.

58 GEOSCIENCES↗

Radiological Monitoring Plan for the Oak Ridge Y-12 National Security Complex: Surface Water

DOE Order 458.1 requires that dose estimates consider contributions from all facilities. In the Y-12 Radiological Monitoring Plan (RMP), surface water is monitored at points that reflect individual facilities, as well as at points that reflect the combined contributions of all facilities. This monitoring plan does not consider other potential routes (i.e., airborne releases and food chains). Thus, a complete determination of total effective dose (TED) cannot be made based on this plan alone. The other routes from Y-12, and all routes from other DOE facilities on the Oak Ridge Reservation (e.g., Oak Ridge National Laboratory (ORNL) and The Heritage Center), must be considered in order to satisfy DOE Order 458.1 requirements. Determination of TED from all sites and pathways is done through the use of dose-assessment models and is documented in the Annual Site Environmental Report. This monitoring plan provides adequate monitoring goals for Y-12 surface water releases to provide input of sufficient sensitivity and accuracy to reliably determine the Y-12 surface water component of the TED. The routine radiological monitoring program is designed to monitor effluents at four types of locations: (1) treatment facilities, (2) other point and area source discharges, (3) instream locations, and (4) production building roof run-off. With this sampling and analysis program, data will be obtained on primary point sources as well as on locations that represent the composite of other potential sources. This plan will be reviewed periodically to determine necessary modifications to the sampling frequencies, parameters, and locations. Modifications, if any, will be based on the analysis of the previous data and its effectiveness in satisfying the objectives of this plan. Appendix A contains graphs of the sum of the DCS fractions for locations and frequencies contained in a previous version of this plan. The data was collected from January 2009 through December 2019. Each sample was analyzed, and each result was divided by the appropriate DCS to compute a DCS fraction. These fractions were summed for all isotopes. According to DOE –STD-1196-2011, the annual average of these sums should be below 1.

54 ENVIRONMENTAL SCIENCES↗

Piezoelectric property of PZT nanofibers characterized by resonant piezo-force microscopy

Nano-piezoelectric materials have drawn tremendous research interest. However, characterization of their piezoelectric properties, especially measuring the piezoelectric strain coefficients, remains a challenge. Normally, researchers use an AFM-based method to directly measure nano-materials’ piezoelectric strain coefficients. But, the extremely small piezoelectric deformation, the influence from the parasitic electrostatic force, and the environmental noise make the measurement results questionable. In this paper, a resonant piezo-force microscopy method was used to accurately measure the piezoelectric deformation from 1D piezoelectric nanofibers. During the experiment, the AFM tip was brought into contact with the piezoelectric sample and set to work at close to its first resonant frequency. A lock-in amplifier was used to pick up the sample’s deformation signal at the testing frequency. By using this technique, the piezoelectric strain constant d 33 of the Lead Zirconate Titanate (PZT) nanofiber with a diameter of 76 nm was measured. The result showed that d 33 of this PZT nanofiber was around 387 pm/V. Meanwhile, by tracking the piezoelectric deformation phase image, domain structures inside PZT nanofibers were identified.

36 MATERIALS SCIENCE↗